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Inversion of Enantioselectivity in Allene Gas versus Allyl Acetate Reductive Aldehyde Allylation Guided by Metal-Centered Stereogenicity: An Experimental and Computational Study

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posted on 2019-09-11, 15:34 authored by Seung Wook Kim, Cole C. Meyer, Binh Khanh Mai, Peng Liu, Michael J. Krische
The use of gaseous allene as an allyl pronucleophile in enantioselective aldehyde reductive coupling is described. Notably, using the same antipode of chiral ligand, (S)-tol-BINAP, an inversion of enantioselectivity is observed for allene versus allyl acetate pronucleophiles. Experimental and computational studies corroborate intervention of diastereomeric π-allyliridium-C,O-benzoate complexes, which arise via allene hydrometalation (from a pentacoordinate iridium hydride) versus allyl acetate ionization (from a square planar iridium species).

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